Conjugated polymers and blends containing carbazole, representation and use thereof

ABSTRACT

The present invention relates to conjugated polymers comprising specific carbazole structural units. The materials according to the invention display steeper current-voltage curves and are therefore better suited to use in organic light-emitting diodes than are comparative polymers which do not contain these units.

Wide-ranging research on the commercialization of display and lightingelements based on polymeric (organic) light-emitting diodes (PLEDs) hasbeen pursued for about 12 years. This development was triggered by thefundamental developments disclosed in EP 423 283 (WO 90/13148).Recently, a first product in the form of a relatively small display (ina shaver from PHILIPS N.V.) has also become available on the market.However, significant improvements are still necessary to make thesedisplays genuinely competitive with the liquid crystal displays (LCDs)which currently dominate the market or to surpass them. In particular,it is necessary to provide polymers for all emission colors (red, green,blue) which meet the requirements of the market (color saturation,efficiency, operating life, voltage, to name the most important).

Various classes of materials have been proposed or developed as polymersfor full-color display elements. Thus, polyfluorene derivatives as aredisclosed, for example, in EP 0842208, WO 99/54385, WO 00/22027, WO00/22026 and WO 00/46321 come into consideration. Furthermore,polyspirobifluorene derivatives as disclosed in EP 0707020, EP 0894107and WO 03/020790 are also possibilities. Polymers which comprise acombination of the two first-named structural elements, as disclosed inWO 02/077060, have also been proposed. In general, polymers comprisingpoly-para-phenylene (PPP) as structural element are possible for suchuse. Apart from the abovementioned classes, “ladder PPPs” (=LPPPs) (e.g.as described in WO 92/18552), polytetrahydropyrenes (e.g. as describedin EP-A-699699) and also PPPs containing ansa structures (e.g. asdescribed in EP-A-690086), for example, also come into question.

As has already been established in some of the abovementioned patentapplications, it is necessary to polymerize particular comonomers intothe appropriate polymers in order to produce all three emission colors(cf., for example, WO 00/46321, DE 10143353.0 and WO 02/077060). It isthen generally possible, starting from a blue-emitting backbone, toproduce the two other primary colors red and green.

Furthermore, it has been reported that the insertion of particulararylamino groups gives an improvement in the properties:

-   -   WO 99/54385 describes polyfluorenes whose efficiency and        operating voltage can be improved by polymerizing derivatives of        triphenylamine, tetraphenyl-p-diamino-benzene or        tetraphenyl-4,4′-diaminobiphenyl into the main chain of the        respective polymers.    -   DE 19846767 describes polyfluorenes in which the efficiency and        operating voltage is likewise improved by incorporating        substituted diarylamino units into the main chain.    -   WO 01/49769 describes polymers containing triarylamino groups in        which at least one of the aryl groups is a heteroaryl group in        general terms. Particular advantages of these polymers are not        described.    -   WO 01/66618 describes copolymers which have not only aryl units        but also specific triarylamino or tetraaryl-p-di-aminoarylene        units in the main chain. The corresponding amino building blocks        comprise trifluoromethyl-substituted phenyls which are bound        directly to the nitrogen atoms, but are not incorporated into        the main chain. An advantage mentioned is that these materials        have, especially in contrast to the derivatives mentioned in the        above-mentioned WO 99/54385, a more readily adjustable HOMO        position and therefore have advantages in use.

Despite the progress cited in the abovementioned patent applications,there is still a considerable need for improvements in such materials.Significant improvements are still necessary in, inter alia, thefollowing fields:

-   -   (1) The current-voltage curves have to become considerably        steeper for a high brightness to be achieved in use at        sufficiently low voltages and thus a higher power efficiency to        be achieved. This is of tremendous importance since, firstly, it        allows the same brightness to be achieved at a lower energy        consumption, which is very important for, in particular, mobile        applications (displays for mobile telephones, PDAs, etc.).        Secondly, higher brightnesses are obtained at the same energy        consumption, which can be of interest for, for example, lighting        applications.    -   (2) Many of the BLUE-emitting polymers described do not display        a saturated deep blue emission, but instead a light blue        emission whose color saturation is not satisfactory for all        applications.

As can be seen from this description of the prior art, there continuesto be a great need for improvements in the field of light-emittingpolymers.

We have surprisingly found that hitherto unknown polymers comprisingparticular carbazole units give considerable improvements, especially inthe two abovementioned areas, i.e. the steepness of the current-voltagecurves (and thus the operating voltage) and the color. These aretherefore subject matter of the present patent application.

The invention accordingly provides conjugated polymers (POLY1)comprising 1-100 mol %, preferably 5-100 mol %, particularly preferably10-100 mol %, of units of the formula (I),

where the symbols and indices have the following meanings:

-   -   R is identical or different on each occurrence and is a        cycloalkyl system which has from 3 to 40 carbon atoms and may be        substituted or unsubstituted, an aromatic or heteroaromatic ring        system which has from 2 to 40 carbon atoms and may be        substituted or unsubstituted or an alkylenearyl,        alkylenecycloalkyl or alkyleneheteroaryl system which has a        linear or branched alkylene chain having from 1 to 16 carbon        atoms and may be substituted or unsubstituted; the aryl,        heteroaryl and cycloalkyl systems can also be part of a larger        fused aromatic or aliphatic ring system; the possible        substituents R¹ can potentially be located on each free        position;    -   Aryl are identical or different on each occurrence and are each        an aromatic or heteroaromatic ring system which has from 2 to 40        carbon atoms and may be substituted or unsubstituted or a        substituted or unsubstituted stilbenylene or tolanylene unit;        the possible substituents R¹ can potentially be located on each        free position;    -   R¹ is identical or different on each occurrence and is a        straight-chain, branched or cyclic alkyl or alkoxy chain which        has from 1 to 22 carbon atoms and in which one or more        nonadjacent carbon atoms may also be replaced by N—R², O, S,        —CO—O—, O—CO—O, where one or more H atoms may also be replaced        by fluorine, an aryl or aryloxy group which has from 5 to 40        carbon atoms and in which one or more carbon atoms may also be        replaced by O, S or N which may also be substituted by one or        more nonaromatic radicals R¹, or Cl, F, CN, N(R²)₂, B(R² )₂,        where two or more radicals R¹ may also together form a ring        system;    -   R^(a) is identical or different on each occurrence and is a        straight-chain, branched or cyclic alkyl or alkoxy chain which        has from 1 to 22 carbon atoms and in which one or more        nonadjacent carbon atoms may also be replaced by N—R², O, S,        —CO—O—, O—CO—O, where one or more H atoms may also be replaced        by fluorine, an aryl or aryloxy group which has from 5 to 40        carbon atoms and in which one or more carbon atoms may also be        replaced by O, S or N which may also be substituted by one or        more nonaromatic radicals R¹, or Cl, F, CN, N(R²)₂, B(R²)₂;    -   R² is identical or different on each occurrence and is H, a        straight-chain, branched or cyclic alkyl chain which has from 1        to 22 carbon atoms and in which one or more non-adjacent carbon        atoms may also be replaced by O, S, —CO—O—, O—CO—O, where one or        more H atoms may also be replaced by fluorine, an aryl group        which has from 5 to 40 carbon atoms and in which one or more        carbon atoms may also be replaced by O, S or N which may also be        substituted by one or more nonaromatic radicals R¹;    -   m is identical or different on each occurrence and is 0, 1 or 2;    -   o is identical or different on each occurrence and is 0, 1 or 2,        with the proviso that o must not be 0 when m=2;    -   r is identical or different on each occurrence and is 0 or 1,    -   z is identical or different on each occurrence and is 0, 1, 2 or        3;    -   the open-line bond indicates the linkage in the polymer; it        should in the present case not be a methyl group.

The carbazole unit can be bound in various ways in the polymer chain:linkage at only one of the points leads to an end group or toincorporation of the structural unit of the formula (I) into the sidechain; linkage at two positions leads to incorporation of the monomerinto the main chain of the polymer; incorporation of the structural unitof the formula (I) into the main chain preferably occurs via the 3,6 or2,7 positions of the carbazole or else via the 2,9 or 3,9 positions if Ris an aromatic or heteroaromatic ring system in the last two cases sothat conjugation of the polymer is retained. The carbazole isparticularly preferably incorporated via the 3,6 or 2,7 positions or viathe 3,9 positions if R is an aromatic or heteroaromatic ring system. Itis very particularly preferably incorporated via the 3,6 or 2,7positions. For the sake of clarity, the numbering of carbazole isindicated in the following structure:

For the purposes of the present invention, conjugated polymers arepolymers which contain mainly sp²-hybridized (or also sp-hybridized)carbon atoms in the main chain, which may also be replaced byappropriate heteroatoms. In the simplest case, this means the presenceof alternating double and single bonds in the main chain. “Mainly” meansthat naturally occurring defects which lead to interruptions to theconjugation do not invalidate the term “conjugated polymers”.Furthermore, a polymer in which, for example, arylamine units such asthe carbazole of the formula (I) or other such units and/or particularheterocycles (i.e. conjugation via N, O or S atoms) and/ororganometallic complexes (i.e. conjugation via the metal atom) arepresent in the main chain is likewise described as conjugated in thepresent patent application. On the other hand, units such as simple(thio)ether bridges, ester linkages, amide or imide linkages would beunambiguously defined as non-conjugated segments.

The polymers of the invention can comprise further structural elementsin addition to the units of the formula (I). These are, inter alia,those which have been disclosed in the above-mentioned patentapplications. Reference will at this point be made, in particular, tothe relatively comprehensive listing in the abovementioned patentapplication WO 02/077060; this is incorporated by reference into thepresent invention. The further structural units can come, for example,from the classes described below:

-   -   1. Structural units which can form the polymer backbone or        BLUE-emitting units:        -   Mention should here firstly be made of units which form            polyphenylenes and structures derived therefrom. These are,            for example, (in each case substituted or unsubstituted)            ortho-, meta- or para-phenylenes, 1,4-naphthylenes,            9,10-anthracenylenes, 2,7-phenanthrenylenes, 1,6- or 2,7- or            4,9-pyrenylenes or 2,7-tetrahydropyrenylenes. Corresponding            heterocyclic “polyphenylene”-forming structures, for example            2,5-thiophenylene, 2,5-pyrrolylene, 2,5-furanylene,            2,5-pyridylene, 2,5-pyrimidinylene or 5,8-quinolinylene are            also possible.        -   Furthermore, more complex units such as the above-mentioned            fluorenes, spiro-9,9′-bifluorenes, multiply bridged units            (e.g. short segments of the abovementioned LPPP polymers)            and also “double fluorene” units (indenofluorenes) are            possible. These, too, may be substituted or unsubstituted.            Corresponding heterocyclic structures in which, for example,            individual ring carbons are replaced by heteroatoms such as            sulfur are also possible here.    -   2. Structural units which improve the charge injection        properties or charge transport properties. This can relate both        to the electron injection or electron transport properties (for        example oxadiazole units) and to the hole injection or hole        transport properties (for example triarylamine units). Here,        reference may once again be made to the comprehensive listing of        such structural units in the above-cited patent application WO        02/077060; this is incorporated by reference into the present        invention. Naphthylarylamines as are described in the        unpublished patent application DE 10249723.0 are likewise        possible for this purpose.    -   3. Structural units which, for example, shift the color of the        emission, thus also alter the band gap of the polymer and thus        generally also alter the charge injection or charge transport        properties:        -   Mention may here be made of, for example, further            heterocyclic compounds such as the structures mentioned in            the abovementioned patent application WO 02/077060 under the            formulae (XX) to (XXXXV).        -   Furthermore, arylene-vinylene or arylene-acetylene            structures such as substituted or unsubstituted            stilbenylenes, tolanylenes, bisstyrylarylenes,            bis(arylacetylene)arylenes may also be mentioned here.        -   Finally, the incorporation of relatively large aromatic            units such as chrysenes, naphthacenes, pentacenes, perylenes            or coronenes can also produce the color-shifting effect.    -   4. Structural units which can emit light with high efficiency        from the triplet state even at room temperature:        -   These are firstly, in particular, compounds containing heavy            atoms, i.e. atoms from the Periodic Table of the Elements            which have an atomic number of greater than 36.        -   Compounds which contain d and f transition metals which meet            the abovementioned conditions are particularly suitable for            this purpose. Very particular preference is given here to            corresponding structural units containing elements of groups            8 to 10 (i.e. Ru, Os, Rh, Ir, Pd, Pt).        -   Various complexes which are described, for example, in the            patent applications WO 02/068435, WO 02/081488, EP 1239526            and the unpublished patent application DE 10238903.9 are            possible as structural units for the polymers of the            invention.

A selection of preferred further units for the polymers of the inventionare listed in the following overview:

The symbols Aryl, R¹ and R² used here are defined analogously to thosedescribed further above.

-   -   n is identical or different on each occurrence and is 0, 1, 2, 3        or 4;    -   p is identical or different on each occurrence and is 0, 1, 2 or        3;    -   q is identical or different on each occurrence and is 0, 1 or 2;    -   M is identical or different on each occurrence and is Rh or Ir;

and the broken-line bonds shown in each case symbolize the linkage inthe polymer; these should in the present case not be methyl groups.

The polymers of the invention are either homopolymers, i.e. they containonly one structure of the formula (I), or copolymers. It can bepreferred that these either contain a plurality of different structuralunits of the formula (I) or contain one or more of the above-describedor above-listed structural units in addition to one or more structuralunit(s) of the formula (I).

The copolymers of the invention can have either random or alternating orblock-like structures or a plurality of these structures can alternatein them. The use of a plurality of different structural elements enablesproperties such as solubility, solid state morphology, color, etc., tobe adjusted.

As stated above, particularly preferred polymers according to theinvention comprise at least 10 mol % of structural units of the formula(I). Specifically for use as emitting material in the PLEDs mentioned, aproportion in this order of magnitude has been found to be useful. Forother applications, e.g. as charge transport layer in organic fieldeffect transistors (OFETs), a significantly higher proportion (up to 100mol %) can also prove to be useful.

In preferred structures of the formula (I), the following applies:

-   -   R is identical or different on each occurrence and is an        aromatic or heteroaromatic ring system selected from among        thiophene, benzothiophene, benzene, pyridine, quinoxaline,        fluorene, spirobifluorene, naphthalene, anthracene, pyrene and        phenanthrene which bears from 0 to 3 substituents R¹ on the free        positions or an alkylenearyl or alkyleneheteroaryl ring system        whose alkylene chain can be linear or branched and has from 1 to        16 carbon atoms and whose aryl and heteroaryl system consists of        the systems described in detail above which bear from 0 to 3        substituents R¹ on the free positions;    -   Aryl is identical or different on each occurrence and is an        aromatic or heteroaromatic ring system which has from 2 to 40        carbon atoms and may be substituted or unsubstituted; the aryl        and heteroaryl systems can also be part of a larger fused        aromatic ring system; the possible substituents R¹ can, if        present, be located on each free position;    -   R¹, R², R^(a), r, z are analogous to the definitions given        above;    -   m is identical or different on each occurrence and is 0 or 1;    -   o is identical or different on each occurrence and is 0, 1 or 2;

the structural unit of the formula (I) is bound into the main chain ofthe polymer via the 3,6 or 2,7 positions or via the 2,9 or 3,9 positionsif R is an aromatic or heteroaromatic unit.

In particularly preferred structures of the formula (I), the followingapplies:

-   -   R is identical or different on each occurrence and is an        aromatic or heteroaromatic ring system selected from among        thiophene, benzothiophene, benzene, pyridine, naphthalene,        anthracene, pyrene and phenanthrene which are unsubstituted or        substituted by a substituent R¹, or a 9,9′-substituted fluorene        or a methylenearyl or methyleneheteroaryl ring system whose aryl        or heteroaryl system comprises the systems described in detail        above which can have the same substitution pattern as the        abovementioned systems;    -   Aryl is identical or different on each occurrence and is an        aromatic or heteroaromatic ring system which has from 2 to 20        carbon atoms and may be substituted or unsubstituted; the aryl        and heteroaryl systems can also be part of a larger fused        aromatic ring system; the possible substituents R¹ can        potentially be located on each free position;    -   R¹, R², R^(a), r are analogous to the definitions given above;    -   m is identical or different on each occurrence and is 0 or 1;    -   o is identical or different on each occurrence and is 0, 1 or 2;    -   z is identical or different on each occurrence and is 0 or 1;

the structural unit of the formula (I) is bound into the main chain ofthe polymer via the 3,6 positions, the 2,7 positions or the 3,9positions if R is an aryl or heteroaryl system.

Particularly preferred structures of the formula (I) are substituted orunsubstituted structures corresponding to the depicted formulae (II) to(XXXI), where the broken-line bonds define the linkage in the polymerand potential substituents are generally not shown in the interests ofclarity:

In very particularly preferred structures of the formula (I), thefollowing applies:

-   -   R is identical or different on each occurrence and is an        aromatic or heteroaromatic ring system selected from among        thiophene, benzothiophene, benzene, naphthalene, anthracene and        phenanthrene which are unsubstituted or substituted by a        substituent R¹, or a benzyl group whose phenyl group can have        the same substitution pattern as the abovementioned systems;    -   Aryl is identical or different on each occurrence and is an        aromatic or heteroaromatic ring system which has from 2 to 20        carbon atoms and may be substituted or unsubstituted; the aryl        and heteroaryl systems can also be part of a larger fused        aromatic ring system; the possible substituents R¹ can        potentially be located on each free position;    -   R¹, R², R^(a), r are analogous to the definitions given above;    -   m is identical or different on each occurrence and is 0 or 1;    -   o is 1 on each occurrence;

where the unit is bound into the polymer chain via the 3,6 or 2,7positions of the carbazole.

Even if this is indicated by the description, it will at this point beonce more stated explicitly that both the structural units of theformula (I) and any units of the formulae (II) to (XXXI) can beunsymmetrically substituted, i.e. different substituents R¹ can bepresent on one unit or these can also be bound in different positions.

The polymers of the invention generally have from 10 to 10 000,preferably from 50 to 5000, particularly preferably from 50 to 2000,repeating units. The polydispersity PD is preferably less than 10,particularly preferably less than 5.

The necessary solubility is achieved, in particular, by means of thesubstituents R¹ both on structures of the formula (I) and on structureswhich, as indicated above, are additionally present in correspondingcopolymers.

In general, it is therefore necessary for at least 2 non-aromatic carbonatoms to be present on average in the substituents per repeating unit.Preference is given to at least 4, particularly preferably at least 8,carbon atoms. Individual carbon atoms among these carbon atoms can alsobe replaced by O or S. This does not rule out a situation where aparticular proportion of repeating units, both of the formula (I) and ofother structural types, bear no further nonaromatic substituents.

Preference is given to no long-chain substituents having more than 12carbon atoms, preferably none having more than 8 carbon atoms,particularly preferably none having more than 6 carbon atoms in a linearchain, being present, so that the morphology of the film is notimpaired.

Nonaromatic carbon atoms are, as in the description of R¹, present inappropriate straight-chain, branched or cyclic alkyl or alkoxy chains.

Preference is therefore also given to polymers according to theinvention in which:

-   -   R¹ is identical or different on each occurrence and is a        straight-chain, branched or cyclic alkyl or alkoxy chain having        from 1 to 10 carbon atoms, where one or more H atoms may also be        replaced by fluorine, or an aryl group which has from 6 to 14        carbon atoms and is also substituted by one or more nonaromatic        radicals R¹.

Particular preference is therefore also given to polymers according tothe invention in which:

-   -   R¹ is identical or different on each occurrence and is a        straight-chain or branched alkyl or alkoxy chain having from 1        to 8 carbon, atoms or an aryl group which has from 6 to 10        carbon atoms and is also substituted by one or more nonaromatic        radicals R¹.

The polymers of the invention have, inter alia, the following surprisingadvantages compared to the abovementioned prior art:

-   -   The current at a given voltage is significantly higher for        comparable polymers when used in PLEDs (cf. data in table 2 and        in FIG. 1), i.e. the current-voltage curve is steeper when the        polymer comprises structural units of the formula (I). This        gives significant advantages, as indicated above, in use since        the objective of producing efficient full-color displays having        a low energy consumption is made possible.    -   The use of polymers according to the invention for the        production of blue emission surprisingly has further advantages:        the emission color becomes deeper (i.e. deep blue) than that        obtained when using analogous polymers without structural units        of the formula (I) (compare, for example, polymers P1 and P2        with polymers C1 and C2).    -   Copolymers of this type can be constructed so that they can emit        all primary colors (red, green, blue).    -   The solubility in organic solvents is generally good, i.e. the        polymers are soluble in concentrations of from 1 to at least 30        g/l (depending on molecular weight) in solvents such as toluene,        xylene, anisole, methylanisole or methyl-naphthalene.

The polymers of the invention are generally prepared by polymerizationof one or more monomers of which at least one comprises structures ofthe formula (I).

There is in principle a relatively large number of differentpolymerization reactions suitable for this purpose; however, the typeslisted below, which all lead to C-C bond formation, have been found tobe particularly useful:

(A) SUZUKI polymerization

(B) YAMAMOTO polymerizations

(C) STILLE polymerizations

(D) HARTWIG/BUCHWALD polymerizations

More precise details regarding the polymerization methods (A) to (D) maybe found, for example, in the unpublished patent application DE10249723.0. In the case of polymers containing double bonds (alkeneunits), the following polymerization methods are also possible:

(E) WITTIG-HORNER polymerization: here, monomers used are firstly abisaldehyde and secondly bisphosphonates or corresponding monoaldehydemonophosphonates and these are reacted under basic conditions in thepresence of solvents to give the corresponding alkene compounds.Reactions of this type which lead to conjugated polymers have beendescribed hitherto:

(i) A. P. Davey et al., Synth. Met. 1999, 103, 2478,

(ii) S.-H. Jin et al., Eur. Polym. J. 2002, 38, 895. The correspondingdescriptions are hereby incorporated by reference into the presentpatent application.

(F) Polymerization by precursor methods (for example sulfoxy precursormethods): starting from bis(chloromethyl) compounds which are able toform a quinodimethane, alkylthiomethyl-chloromethyl intermediates arefirstly obtained by substitution on one side. The sulfoxide is obtainedfrom these intermediates by oxidation. This precursor monomer is reactedunder the conditions of the Gilch polymerization, with the effectivemonomer being an alkylsulfoxyquinodimethane. The relativelytemperature-stable precursor polymer obtained in this way is apoly(arylene-alkylsulfoxyethylene) which when simply heated at below200° C. eliminates alkylsulfinic acid to form the fully conjugatedpolymer. These reactions are described, inter alia, in the followingreferences: (i) WO 00/35987 (ii) A. Issaris, D. Vanderzande,Macromolecules 1998, 31, 4426-4431. The corresponding descriptions arehereby incorporated by reference into the present patent application.

The ways in which the polymerizations can preferably be carried out andthe ways in which the polymers can then be separated off from thereaction solution and be purified are described, for example, in theunpublished patent application DE 10249723.0.

To be able to prepare the polymers of the invention, for example by theabovementioned methods, the corresponding monomers are required, asdescribed.

In the case of structures of the formula (I), these can be obtained, forexample, as described in the following:

-   -   The synthesis of 3,6-dibromocarbazole is carried out by        bromination of carbazole, as described in the literature: Smith        et al., Tetrahedron 1992, 48, 7479-7488.    -   The synthesis of 2,7-dibromocarbazole is carried out by building        up the carbazole, as described in the literature: Tidwell et        al., Eur. J. Med. Chem. 1997, 32, 781-793.    -   An appropriate functionalization which makes use as monomers        possible (i.e., for example, introduction of halogen end groups)        can either be carried out on the precursors or as last step on        the previously fully constructed monomeric skeleton. Both        variants have both advantages and disadvantages, depending on        the desired target structure.    -   The functions can be present beforehand if they do not react or        react only sluggishly in the reaction to form the appropriate        monomer. This can, for example, be the case for a simple        substitution reaction or when different reactivities (e.g.        iodine versus bromine, or bromine versus chlorine) can be        exploited. Thus, for example, a monomer which gives the        structural units of the formula (III) can be prepared by        exploiting the selectivity of iodine compared to bromine, as        described in example 2.    -   On the other hand, it can also be advantageous (e.g. in the case        of existing substitution or directing radicals) firstly to build        up the N-substituted carbazole skeleton and to introduce the        halide in a last step. It is thus possible, for example, to        introduce bromine in the 3 and 6 positions of the carbazole in        structures of the formula (II) (for example by means of a mild        NBS bromination, cf., for example, Creason et al., J. Org.        Chem., 1972, 37, 4440), when a substituent is present in the        para position on the N-aryl substituent. As indicated above,        this process can generally be employed in the presence of (i)        appropriate blocking substituents, (ii) appropriate directing        radicals or (iii) activated or deactivated heterocycles even for        further structures of the formula (I).    -   The N-alkylation or N-benzylation of carbazoles is known in the        literature. Likewise, N-alkylarylcarbazoles and        N-cycloalkylcarbazoles can be obtained. The synthesis is carried        out by reaction of carbazole with an alkylating agent under        basic conditions, as described, for example, in: M. E. Wright,        M.-J. Jin, J. Org. Chem. 1989, 54, 965-968.    -   The N-arylation of carbazole can be carried out by the

Hartwig-Buchwald method and is described for carbazole in, for example:M. Watanabe et al., Tetrahedron Lett. 2000, 41, 481-483.

-   -   Starting from the halide derivatives produced in this way,        corresponding bisboronic acid derivatives or bisstannane        derivatives (which are required for the abovementioned        polymerization processes of the types A and C) can be prepared        by standard methods. These methods are well known to those        skilled in the art and generally comprise replacing the halogen        present by a metal (e.g. magnesium, lithium) and then reacting        the product with a boric ester compound or a trialkyltin halide        compound. For the preparation of boronic acid derivatives,        catalytic processes involving direct reaction of the halides        with, for example, diboranes in the presence of palladium are        also known. Comparable reactions are also known for the        corresponding tin compounds. Corresponding        monohalide-monoboronic acid derivatives or        monohalide-monostannane compounds are also obtainable if a        suitable stoichiometry is employed.    -   The corresponding bisaldehyde derivatives required for the        abovementioned polymerization process of the type E can likewise        be prepared from the halide derivatives. This method is well        known to those skilled in the art and generally comprises        replacing the halogen present by a metal (e.g. magnesium,        lithium) and then reacting the product with a formic acid        derivative (e.g. dimethyl-formamide).    -   The corresponding phosphonate derivatives which are required for        the abovementioned polymerization process of the type E can be        produced from the corresponding methylene halide compounds which        are then reacted with trialkyl esters of phosphorous acid. Such        processes are well known to those skilled in the art.

The synthesis of the further monomers which lead to structures which donot correspond to the formula (I) but have been described above iscomprehensively described in the abovementioned patent applications andpatents.

A good overview is given by the patent application WO 02/077060; thedetails given there on this subject are incorporated by reference intothe present patent application.

The polymers obtained in this way can be used as single components inapplications described in more detail below. They can also be used asblends (mixtures of polymers with further polymeric or low molecularweight components). The invention thus also provides a blend of thepolymer of the invention with other polymers which can be, for example,conjugated or non-conjugated.

Furthermore, it is known and prior art that blends (mixtures) ofnonconjugated polymers such as PVK (polyvinylcarbazole) with lowmolecular weight metal complexes which allow transfer of singletexcitons to triplet excitons and can emit light from the triplet stateresult in efficient electroluminescence of the metal complex. Suchmixtures are described, for example, by F.-C. Chen et al., (Appl. Phys.Lett. 2002, 80, 2308-2310). Compared to metal complexes which have to bevapor deposited in a complicated and expensive process to allow them tobe used, these blends offer the advantage that they can be processedmore simply and cheaply from solution. However, the operating voltagesfor these systems are very high, which results in a very low powerefficiency.

Blends of low molecular weight metal complexes which emit light from thetriplet state with conjugated polymers have likewise been described inthe literature. T. F. Guo et al. (Organic Electronics 2000, 1, 15) andD. F. O'Brien et al. (Synth. Met. 2001, 116, 379) describe good quantumefficiencies when using blends of a platinum-porphyrin complex withpolyfluorenes; in both cases, the efficiencies are significantly lowerthan in the case of comparable devices made up of small molecules. W.Zhu et al. (Appl. Phys. Lett. 2002, 80, 2045-2047) describe a blend of asoluble iridium-phenylpyridine complex with a poly-para-phenylene.Better but still relatively low quantum efficiencies were measured inthis case. In particular, very high voltages were required for thissystem, and these would stand in the way of an industrial application.Thus, there continues to be a great need for improvement here, too.

It has surprisingly been found that hitherto unknown blends (i.e.mixtures) of the polymers described below with dendrimers and/or lowmolecular weight compounds and possibly but not necessarily a furtherconjugated or nonconjugated polymer give unexpected advantages in theapplication here. Like the polymers POLY1 of the invention themselves,these novel blends display steeper current-voltage curves and thus loweroperating voltages.

The invention thus further provides blends (mixtures) comprising

-   -   (A) 5-99.5% by weight of. at least one conjugated polymer        (POLY2) comprising 1-100 mol %, preferably 5-100 mol %,        particularly preferably 10-100 mol %, of units of the formula        (XXXII),        where the symbols and indices have the following meanings:    -   R³ is identical or different on each occurrence and is a linear        or branched alkyl chain which has from 1 to 40 carbon atoms and        may be substituted or unsubstituted, a cycloalkyl system which        has from 3 to 40 carbon atoms and may be substituted or        unsubstituted, an aromatic or heteroaromatic ring system which        has from 2 to 40 carbon atoms and may in each case be        substituted or unsubstituted or an alkylenearyl,        alkylenecycloalkyl or alkyleneheteroaryl system which may be        substituted or unsubstituted; the possible substituents R¹ can        potentially be located on each free position; the aryl and        heteroaryl systems can also be part of a larger fused aromatic        ring system;        the further symbols and indices are as defined above under the        formula (I);

and

-   -   (B) 0.5-95% by weight of at least one organic or organo-metallic        dendrimer or at least one low molecular weight molecule having a        molecular weight in the range <10 000 (COMP1) which in a pure or        dilute film is capable of fluorescence or phosphorescence and        which has adequate solubility in suitable solvents, preferably        toluene, xylene, anisole, THF, methylanisole or        methylnaphthalene, to be able to be processed in the blend        together with the polymer from a solution in this solvent.

The proportion of the dendrimer or the low molecular weight compound inthe blend is preferably from 0.5 to 80% by weight, particularlypreferably from 1 to 50% by weight, in particular from 2 to 25% byweight.

The proportion of the polymer (POLY2) in the blend is preferably from 20to 99.5% by weight, particularly preferably from 50 to 99% by weight, inparticular from 75 to 98% by weight.

For the present purposes, a dendrimer is a highly branched compoundwhich is made up of a multifunctional core to which branched monomersare bound in a regular arrangement so as to give a tree-like structure.Both the core and the monomers can have any branched structures whichmay consist of purely organic units and of organometallic compounds orcoordination compounds. For the present purposes, a dendrimer is ingeneral terms as described in, for example, M. Fischer, F. Vögtle,Angew. Chem., Int. Ed. 1999, 38, 885-905.

The structural unit of the formula (XXXII) is a constituent ofhomopolymers and copolymers as described above for the structural unitof the formula (I). Here too, the same monomers like, for example, themonomers M1 to M23 indicated in the examples are possible. The synthesisof these polymers can be carried out by the above-described methods. Ithas been found that in the case of blends which emit light from thesinglet state, a proportion in the region of 10 mol % of structuralunits of the formula (XXXII) in the polymer POLY2 gives good results.For other applications, in particular for blends which emit light fromthe triplet state, it can be preferable to have a proportion of greaterthan 10 mol % of structural units of the formula (XXXII) in the polymerPOLY2.

Blends which emit light from the triplet state preferably have aproportion of 20-100 mol % of structural units of the formula (XXXII) inthe polymer POLY2. A proportion of 30-100 mol % of structural units ofthe formula (XXXII) is particularly preferred for these blends.

In preferred polymers POLY2, the following applies:

-   -   R³ is identical or different on each occurrence and is a linear        or branched alkyl chain which has from 1 to 40 carbon atoms and        may be substituted or unsubstituted, an aromatic or        heteroaromatic ring system selected from among thiophene,        benzothiophene, benzene, pyridine, quinoxaline, fluorene,        spirobifluorene, naphthalene, anthracene, pyrene and        phenanthrene which bears from 0 to 3 substituents R¹ on the free        positions or an alkylenearyl or alkyleneheteroaryl ring system        whose alkylene chain may be linear or branched and has from 1 to        16 carbon atoms and whose aryl or heteroaryl system comprises        the systems described in detail above which bear from 0 to 3        substituents R¹ on the free positions;        and the further symbols and indices are as described above for        preferred structures of the formula (I).

In particularly preferred polymers POLY2, the following applies:

-   -   R³ is identical or different on each occurrence and is a linear        or branched alkyl chain which has from 2 to 30 carbon atoms and        may be substituted or unsubstituted, an aromatic or        heteroaromatic ring system selected from among thiophene,        benzothiophene, benzene, pyridine, naphthalene, anthracene,        pyrene and phenanthrene which are unsubstituted or substituted        by a substituent R¹, or a 9,9′-substituted fluorene or a        methylenearyl or methylene-heteroaryl ring system whose aryl or        heteroaryl system comprises the systems described in detail        above which can have the same substitution pattern as the        systems mentioned above;        and the further symbols and indices are as described above for        particularly preferred structures of the formula (I).

In very particularly preferred polymers POLY2, the following applies:

-   -   R³ is identical or different on each occurrence and is a linear        or branched alkyl chain which has from 3 to 20 carbon atoms and        may be substituted or unsubstituted, an aromatic or        heteroaromatic ring system selected from among thiophene,        benzothiophene, benzene, naphthalene, anthracene and        phenanthrene which are unsubstituted or substituted by a        substituent R¹, or a benzyl ring system whose phenyl group can        have the same substitution pattern as the systems mentioned        above;        and the further symbols and indices are as defined above for        very particularly preferred structures of the formula (I).

The dendrimers or low molecular weight compounds COMP1 used in the blendcan be selected from a wide variety of classes of substances. Preferenceis given here to blends of polymers POLY2 with one or more dendrimers orone or more low molecular weight compounds which make a transfer ofsinglet excitons to triplet excitons possible and which can emit lightwith high efficiency from the triplet state even at room temperature:these are firstly, in particular, compounds which contain heavy atoms,i.e. atoms from the Periodic Table of the Elements having an atomicnumber of greater than 36. Compounds containing d and f transitionmetals which meet the above-mentioned condition are particularly usefulfor this purpose. Very particular preference is given here to structuralunits of this type containing elements of groups 8 to 10 (i.e. Ru, Os,Rh, Ir, Pd, Pt). Possible low molecular weight structural units of thistype are, for example, various complexes which are described, forexample, in the patent applications WO 02/068435, WO 02/081488, EP1239526 and the unpublished patent application DE 10238903.9. Dendrimerstructures which can be used for this purpose are complexes asdescribed, for example, in the patent applications WO 99/21935, WO01/059030 and WO 02/066552. The corresponding descriptions are herebyincorporated by reference into the present patent application.

The blends of the invention have, inter alia, the following surprisingadvantages compared to the abovementioned prior art:

-   -   The current at a given voltage is significantly higher for        comparable blends when used in PLEDs (cf. data in table 3), i.e.        the current-voltage curve is steeper when the polymer component        of the blend comprises structural units of the formula (XXXII).        This gives significant advantages, as indicated above, in use        since the objective of producing efficient full-color displays        having a low energy consumption is made possible.    -   The use of blends according to the invention comprising        components which emit from the triplet state surprisingly has        the following further advantage: the energy transfer from the        polymer to the metal complex occurs more efficiently in a blend        according to the invention than in comparable blends which do        not contain any polymers POLY2, which leads to more efficient        emission by the metal complex (cf. data in table 3).    -   The solubility in organic solvents is generally good, i.e. the        polymers POLY1 and blends are soluble in concentrations of from        1 to at least 30 g/l (depending on molecular weight) in solvents        such as toluene, xylene, anisole, methylanisole or        methylnaphthalene. Possible solvents and solvent mixtures are,        for example, those described or cited in the patent application        WO 02/072714. Although this is not in itself an improvement over        the prior art, it is important that this property is maintained        in the introduction of new structures.

The polymers of the invention or the blends of the invention can be usedin PLEDS. The way in which PLEDs can be produced is described,comprehensively as a general method in DE 10249723.0, which can beadapted appropriately for each individual case.

-   -   As stated above, the polymers of the invention are very        particularly useful as electroluminescence materials in PLEDs or        displays produced in this way.

As stated above, the polymers and blends of the invention are veryparticularly useful as electroluminescence materials in PLEDs ordisplays produced in this way.

For the purposes of the invention, electroluminescence materials arematerials which can be used as active layer in a PLED. Active layermeans that the layer is capable of emitting light on application of anelectric field (light-emitting layer), and/or that it improves theinjection and/or transport of the positive and/or negative charges(charge injection layer or charge transport layer).

The invention therefore also provides for the use of a polymer or blendaccording to the invention in a PLED, in particular aselectroluminescence material.

The invention thus likewise provides a PLED comprising one or moreactive layers, wherein at least one of these active layers comprises oneor more polymers and/or blends according to the invention. The activelayer can, for example, be a light-emitting layer and/or a transportlayer and/or a charge injection layer.

PLEDs are employed, for example, as self-illuminating display elementssuch as control lamps, alphanumeric displays, multi-color or full-colordisplays, information signs and in opto-electronic couplers.

The present patent application and also the further examples below aredirected at the use of polymers or blends according to the invention inPLEDs and the corresponding displays.

Despite this restriction of the description, a person skilled in the artwill readily be able, without having to make a further inventive step,to utilize the polymers or blends according to the invention for furtherapplications in other electronic devices, e.g. for organic integratedcircuits (O-ICs), in organic field effect transistors (OFETs), inorganic thin film transistors (OTFTs), for organic solar cells (O-SCs),nonlinear optics or organic laser diodes (O-lasers), to name only a fewapplications. In the case of O-ICs and OFETs in particular, it ispossible to use appropriate polymers according to the invention whichhave a relatively high proportion of structural elements of the formula(I) (preferably a proportion of more than 20 mol %).

The invention is illustrated by the following examples without beingrestricted thereby.

EXAMPLES

Part A: Synthesis of the Monomers and Blend Constituents:

A1: Monomers for Units of the Formula (I)

3,6-Dibromocarbazole and 2,7-dibromocarbazole were synthesized asdescribed by Smith et al., Tetrahedron 1992, 48, 7479-7488, and Tidwellet al., Eur. J. Med. Chem. 1997, 32, 781-793.3,6-Dibromo-N-ethylhexylcarbazole (=EHC) were synthesized as describedby J. Huang et al., Macromolecules 2002, 35, 6080-6082.

The structural integrity of all products was demonstrated by means of ¹HNMR spectroscopy, and the purity of the products was determined by meansof HPLC.

Example 1 N-(4-tert-Butylphenyl)-3,6-dibromocarbazole (EM1)

A degassed solution of 17 g (80 mmol) of 1-bromo-4-tert-butyl-benzene in1500 ml of xylene was saturated with N₂ for 1 hour. The solution wassubsequently admixed with 500 g of glass spheres (6 mm) and 15.37 g (160mmol) of K₃PO₄ and was stirred for another 15 minutes. After stirringfor 5 minutes, the reaction mixture was admixed with 90 mg (0.4 mmol) ofpalladium(II) acetate, 400 mg (2 mmol) of P(t-Bu)₃ and 10 g (60 mmol) ofcarbazole. The reaction mixture was refluxed for 4 hours. After cooling,the solvent was removed under reduced pressure and the product wasrecrystallized from n-hexane. Purity according to HPLC: 99.6%. Yield: 13g (68%).

¹H-NMR (CDCl₃, 500 MHz) : 1.42 (s, 9 H), 7.26 (t, J₃=7.7 Hz, 2 H), 7.40(m, 4 H), 7.48 (d, J=8.7 Hz, 2 H), 7.59 (d, J=8.7 Hz, 2 H), 8.14 (d, J=8Hz, 2 H).

12 g (40 mmol) of N-(4-tert-butylphenyl)carbazole and 70 g of silica geltogether with 700 ml of CH₂Cl₂ were placed in a reaction vessel. 13 g(80 mmol) of NBS were subsequently added a little at a time to thesolution at 0° C. while protecting it from light and the mixture wasstirred at this temperature for 2 hours. The mixture was admixed with100 ml of water and extracted with CH₂Cl₂. The organic phase was driedover MgSO₄ and the solvent was removed under reduced pressure. Theproduct was stirred with hot hexane and filtered. Yield: 11 g (66%) ofcolorless powder which had an HPLC purity of 99.2%.

¹H-NMR (CDCl₃, 500 MHz) : 1.42 (s, 9 H), 7.25 (d, J=8.7 Hz, 2 H), 7.39(d, J=8.3 Hz, 2 H), 7.48 (dd, J₃=8.7 Hz, J₄=2 Hz, 2 H), 7.61 (d, J=8.7Hz, 2 H), 8.18 (d, J₄=8 Hz, 2 H).

Example 2 N-(4-tert-Butylphenyl)-2,7-dibromocarbazole (EM2)

A degassed solution of 489.5 mg (0.156%) of copper(I) chloride and 906mg (1%) mmol) of 1,10-phenanthroline in 100 ml of toluene were saturatedwith N₂ for 1 hour and heated to 130° C. The solution was subsequentlyadmixed with 16.2 g (50 mmol) of 2,7-dibromocarbazole and 13.2 g (50mmol) of 1-iodo-4-tert-butylbenzene and heated at 180° C. for 2 hours.After cooling, the mixture was admixed with 180 ml of water, the organicphase was separated off and the solvent was removed under reducedpressure. The product was recrystallized from n-hexane. Yield: 13 g(59%). Purity according to HPLC: 99.5%

¹H-NMR (CDCl₃, 500 MHz): 1.43 (s, 9 H), 7.21 (t, J=7.7 Hz, 2 H), 7.23(t, J=7.7 Hz, 2 H), 7.32 (dd, J₃=8.7 Hz, J₄=1.6 Hz, 2 H), 7.50, (d,J₄=1.6 Hz, 2 H), 7.89 (d, J=8.7 Hz, 2 H).

Example 3 N-(4-tert-Butylphenyl)methyl-3,6-dibromocarbazole (EM3)

In a 250 ml one-neck flask provided with a reflux condenser, 990 mg(41.2 mmol) of NaH were suspended in 80 ml of dry DMF under protectivegas. 10 g (30.8 mmol) of 3,6-dibromocarbazole in 80 ml of DMF were addeddropwise to this reaction mixture at RT over a period of 20 minutes. Asolution of 4-(tert-butyl)-benzyl bromide in 50 ml of DMF wassubsequently added dropwise and the mixture was heated at 60° C. for 8hours. After cooling to room temperature, 300 ml of water and 200 ml ofethyl acetate were carefully added. The organic phase was washed with4×50 ml of H₂O, then dried over MgSO₄ and the solvents were removedunder reduced pressure. The pure product was obtained byrecrystallization from n-hexane. Yield: 11 g (78%); HPLC purity: 99.4%.

¹H-NMR (CDCl₃, 500 MHz): 1.22 (s, 9 H), 5.42 (s, 2 H), 6.98 (d, J=8.7Hz, 2 H), 7.22 (d, J=8.7 Hz, 2 H), 7.26 (d, J=8.4 Hz, 2 H), 7.50 (dd,J₃=8.4 Hz, J₄=2 Hz, 2 H), 8.14 (d, J₄=2 Hz, 2 H)

Example 4 N-(4-tert-Butylphenyl)methyl-2,7-dibromocarbazole (EM4)

The synthesis was carried out using a method analogous to example 3,starting from 2,7-dibromocarbazole. The yield was 94%.

¹H-NMR (CDCl₃, 500 MHz): 1.21 (s, 9 H), 5.41 (s, 2 H), 6.97 (d, J=8.7Hz, 2 H), 7.23 (d, J=8.7 Hz, 2 H), 7.33 (dd, J₃=8.7 Hz, J₄=1.6 Hz, 2 H),7.51 (d, J₄=1.6 Hz, 2 H), 7.88 (d, J=8.7 Hz, 2 H).

Example 5 N-(4-tert-Butylphenyl)carbazole-3,6-biscarbaldehyde (EM5)

In a 250 ml three-necked flask, 32 mmol of EM1 were dissolved in 100 mlof dry THF under protective gas. After cooling to −78° C., precooledBuLi (80 mmol, 15% strength) was injected into the solution via a septumwhile stirring. Cooling was maintained and after 2 hours 5.2 ml of DMFwere added dropwise at −60° C. The mixture was allowed to warm to RT andstirring was continued overnight. 200 ml of ice water were subsequentlyadded carefully and the mixture was extracted with chloroform. Theorganic phase was dried over MgSO₄ and the solvents were removed underreduced pressure. The pure product was obtained by recrystallizationfrom n-hexane. Yield: 8 g (68%). Purity according to HPLC: 99.1%

¹H-NMR (CDCl₃, 500 MHz): 1.34 (s, 9 H), 6.38 (d, J=8.1 Hz, 2 H), 6.82(d, J=8.7 Hz, 2 H), 7.04 (d, J=8.1 Hz, 2 H), 7.18 (d, J=8.7 Hz, 2 H),7.31 (d, J=8.7 Hz, 2 H), 9.2 (s, 2 H).

Example 63,6-Bis[2-(4-bromophenyl)ethenyl]-N-(4-tert-butyl-phenyl)carbazole (EM6)

32 mmol of diethyl 4-bromobenzylphosphonate were dissolved in 90 ml ofdry DMF under protective gas and cooled to 5° C. 60 mmol of NaO^(t)Buwere subsequently added in small portions, with the temperature notrising above 5° C. After 30 minutes, 14.7 mmol of EM5 in 25 ml of DMFwere added dropwise at 5° C. and the mixture was stirred for a further30 minutes at this temperature. The reaction mixture was cooled, 25 mlof 4M HCl were added dropwise and the precipitate was filtered off withsuction. 100 ml of water were subsequently added carefully and themixture was extracted with CH₂Cl₂. The organic phase was dried overMgSO₄ and the solvents were removed under reduced pressure. The pureproduct was obtained by recrystallization from ethyl acetate/CH₂Cl₂mixture (1:1). Yield: 79 g (90%). Purity according to HPLC: 99.6%

¹H-NMR (CDCl₃, 500 MHz): 1.33 (s, 9 H), 6.34 (d, J=8.1 Hz, 2 H), 7.02(d, J=8.1 Hz, 2 H), 7.08 (d, J=16.4 Hz, 2 H), 7.30 (d, J=16.4 Hz, 2 H),7.37 (d, J=8.3 Hz, 2 H), 7.41 (d, J=8.3 Hz, 4 H), 7.48 (d, J=8.3 Hz, 4H), 7.64 (dd, J₃=8.3 Hz, J₄=1.6 Hz, 2 H), 8.23 (d, J₄=1.6 Hz, 2 H).

Further monomers of the formula (I) or the formulae (II) to (XXXI) weresynthesized by methods analogous to the abovementioned examples.

A2: Monomers for Further Units

The synthesis of the further monomers M1 to M23 has been described indetail in WO 02/077060 and the references cited therein. The monomersare shown once again below so as to give a better overview:

A3: Low Molecular Weight Compounds for Use in Blends

The low molecular weight compounds used here by way of example in blendsaccording to the invention are, for example, soluble derivatives oftris(phenylpyridyl)iridium(III). The synthesis of these compounds hasbeen described in the patent application WO 02/081488 and in theunpublished patent application DE 10238903.9. However, it will beclearly stated once more at this point that the blends according to theinvention are not restricted to these low molecular weight compoundsused here, but the nonpolymeric components can be the compounds COMP1specified in more detail above. To give an overview, the two iridiumcomplexes used here by way of example are shown once more below:

Part B: Preparation of the Polymers and Blends

Synthesis of Polymer P1

3.2026 g (4 mmol) of monomer M2, 1.6237 g (2.4 mmol) of monomer M7,0.6069 g (0.8 mmol) of monomer M9, 0.3770 g (0. 8 mmol) of EM1 and 3.91g (2.125 equivalents) of potassium phosphate hydrate were dissolved in37.5 ml of dioxane, 12.5 ml of toluene and 6.8 ml of H₂O (all solventsoxygen-free). The reaction solution was degassed by means of argon for30 minutes at 40° C. 0.45 mg (0.025%) of Pd(OAc)₂ and 3.65 mg (0.15%) ofP(o-tolyl)₃ were then added as catalyst and the solution was refluxedunder an argon atmosphere for 1.5 hours. The highly viscous polymersolution was diluted with 20 ml of toluene. The end-capping was thencarried out by adding 100 mg of benzene-boronic acid, refluxing for 45minutes, then adding 0.2 ml of bromobenzene and refluxing for a further45 minutes. The polymer solution was stirred with 100 ml of 0.01%strength aqueous NaCN solution at 60° C for 3 hours. The phases werethen separated and the organic phase was washed with 4×100 ml of H₂O.The polymer was precipitated by addition of twice the volume of methanoland filtered. Further purification was effected by dissolution in 200 mlof toluene at 60° C. under argon, filtration through a glass frit andrenewed precipitation by addition of twice the volume of methanol. Thepolymer was filtered off and dried under reduced pressure. 4.85 g (96%of theory) of polymer were isolated; M_(w)=578 000, M_(n)=156 000,polydispersity=3.7.

Synthesis of Polymer P2

The polymer was synthesized by a method analogous to that for polymer P1using 3.2026 g (4 mmol) of monomer M2, 1.0825 g (1.6 mmol) of monomerM7, 0.6069 g (0.8 mmol) of monomer M9, 0.8185 g (0.8 mmol) of monomerM19, 0.3658 g (0.8 mmol) of EM4 and 3.91 g (2.125 equivalents) ofpotassium phosphate hydrate in 25 ml of dioxane, 25 ml of toluene and6.8 ml of H₂O. 4.57 g (92% of theory) of polymer were isolated M_(w)=791000, M_(n)=239 000, polydispersity=3.3.

Further polymers were prepared by methods analogous to that describedfor P1. The chemical properties are summarized in table 1. Somecomparative polymers (which do not contain any units of the formula (I))were also prepared. These, too, are shown in the table.

Preparation of the Blends

The blends are synthesized by dissolving the polymer together with thedendrimer or the low molecular weight compound in the desired ratio in asuitable solvent such as toluene, xylene, THF, chlorobenzene or anisoleand processing the solution directly without isolation of the blend insolid form. All polymers and blends were also examined for use in PLEDs.The way in which PLEDs can be produced has firstly been mentioned aboveand is described in part C.

Some device properties (color, efficiency and operating voltage) arealso shown in table 1.

The current-voltage characteristics of some polymers are documented intable 2 and FIG. 1. It can readily be seen here that the curves risesignificantly more steeply in the case of the polymers according to theinvention and the current at a given voltage is significantly higher inthe case of the polymers and blends according to the invention than inthe case of the comparative polymers or blends comprising unconjugatedpolymers with low molecular weight compounds according to the prior art.

In table 3, some device properties (color, efficiency and operatingvoltage) of blends according to the invention are shown and comparedwith blends corresponding to the prior art. TABLE 1Electroluminescence*** Proportion of monomers in the polymerization [%]GPC** Voltage Visco.***** Monom. 3 M_(n) Max. at 100 CIE Gel Polymer(+possibly M_(w) (·1000 λ_(max) eff Cd/m² coordinates**** temp. (type)*Monom. 1 Monom. 2 mono. 4) EM (·1000 g/mol) g/mol) [nm] [Cd/A] [V] (x/y)[° C.] P1 (S) 50% of 30% of 10% of M9 10% of EM1 578 156 449 3.10 4.70.15/0.12 <0° C. M2 M7 P2 (S) 50% of 20% of 10% of 10% of EM4 791 239455/ 2.12 5.8 0.18/0.25 <0° C. M2 M7 M9, 10% 482 of M19 P3 (S) 50% of40% of 10% of EM2 624 132 433/ 2.25 4.4 0.16/0.10 <0° C. M2 M1 449 P4(S) 50% of 50% of EM3 298 61 427 1.24 7.9 0.16/0.06 M2 P5 (S) 50% of 30%of 10% of 10% of EM3 824 204 454/ 5.06 3.6 0.17/0.25 <0° C. M2 M7 M19481 P6 50% of 50% of EHC^(b) 298 61 (S)^(a) M2 P7 50% of 50% of EM1 30879 (S)^(a) M2 P8 50% of 40% of 10% of EHC^(b) 764 200 (S)^(a) M2 M1 P950% of 10% of 10% of M9 30% of EHC^(b) 350 114 (S)^(a) M2 M1 C1 (S) 50%of 40% of 10% of M9 1190 199 464 3.42 4.9 0.16/0.17 <0° C. M2 M7 C2 (S)50% of 30% of 10% of 464 126 459/ 5.31 4.2 0.18/0.29 <0° C. M2 M7 M9,10% 484 of M19 C3 (S) 50% of 50% of 207 63 433/ 1.38 4.8 0.16/0.11 <0°C. M2 M1 449 C4 (S) 50% of 40% of 10% of 520 170 461/ 3.99 4.1 0.16/0.25<0° C. M2 M7 M19 483*S = Prepared by Suzuki polymerization (cf. ex. P1), Y = prepared byYamamoto polymerization**GPC measurements in THF; 1 ml/min, Plgel 10 μm Mixed-B 2 × 300 × 7.5mm², 35° C., RI detection was calibrated against polystyrene***For production of the polymer LEDs, see part C****CIE coordinates: chromaticity coordinates of the CommissionInternationale de 1′Eclairage*****Solutions of the polymer (10 mg/ml) in toluene were heated to 60°C., cooled at 1° C./minute and the viscosity was measured in aBrookfield LVDV-III rheometer (CP-41). A sharp increase in viscosityoccurs at the gel temperature determined in this way.^(a)Polymer P6 to polymer P9 were examined only in blends with tripletemitters (cf. table 3).^(b)EHC = 3,6-dibromo-N-ethylhexylcarbazole

TABLE 2 Current density (mA/cm²) at a voltage of Polymer 2 V 3 V 4 V 5 V6 V P5 0 0.3 4.6 18.3 51.7 C2 0 0.2 2.6 12.3 38.0 C4 0 0.1 1.7 6.5 16.4

Comparison of the current at different voltages (for the example of apolymer according to the invention and two polymers which have a similarcomposition but do not contain any structural units of the formula (I)).

FIG. 1 shows a comparison of the current-voltage curves for the polymerP5 according to the invention (containing 10% of carbazole) with thecomparative polymer C2 (containing 10% of the hole conductor M9 but nocarbazole) and the comparative polymer C4 (containing no other holeconductor nor any carbazole). TABLE 3 Electroluminescence* Blendcomposition CIE1931 Iridium Proportion of Ir Max. eff. Voltage atcoordinates** Blend Polymer complex complex [%] λ_(max) [nm] [cd/A] 100Cd/m² [V] (x/y) B1 P5 Ir1 8 534 9.29 5.90 0.40/0.58 B2 P5 Ir2 8 604 6.2210.62 0.59/0.41 B3 P6 Ir1 8 532 9.23 5.88 0.38/0.60 B4 P7 Ir1 8 53212.82 6.92 0.38/0.60 B5 P7 Ir1 20 532 14.49 5.87 0.38/0.60 B6 P6 Ir2 8604 6.27 10.60 0.50/0.61 B7 P8 Ir2 8 611 4.42 6.41 0.62/0.38 B8 P8 Ir220 614 7.53 4.35 0.62/0.38 B9 P9 Ir2 8 606 6.62 6.91 0.60/0.40 CB1 C3Ir1 8 529 0.65 6.33 0.36/0.55 CB2 C3 Ir2 8 605 0.40 6.70 0.60/0.39 CB3PVK*** Ir1 8 520 7.13 13.71 0.37/0.60 CB4 PVK*** Ir2 8 600 3.64 13.410.58/0.42*For the production of the polymer LEDs, see part C**CIE coordinates: chromaticity coordinates of the CommissionInternationale de 1′Eclairage of 1931***PVK = poly(vinylcarbazole)Part C: Production and Characterization of LEDs:

All polymers and blends were examined for use in PLEDs. These PLEDs werein each case two-layer systems, i.e.substrate//ITO//PEDOT//polymer//cathode. PEDOT is a polythiophenederivative (Baytron P from H. C. Stark, Goslar). As cathode, Ba/Ag (bothfrom Aldrich) was used in all cases. The way in which PLEDs can beproduced is described in detail in DE 10249723.0 and the referencescited therein.

1. A conjugated polymer (POLY1), characterized in that it comprises1-100 mol % of units of the formula (I),

where the symbols and indices have the following meanings: R isidentical or different on each occurrence and is a cycloalkyl systemwhich has from 3 to 40 carbon atoms and may be substituted orunsubstituted, an aromatic or heteroaromatic ring system which has from2 to 40 carbon atoms and may be substituted or unsubstituted or analkylenearyl, alkylenecycloalkyl or alkyleneheteroaryl system which hasa linear or branched alkylene chain having from 1 to 16 carbon atoms andmay be substituted or unsubstituted; the aryl, heteroaryl and cycloalkylsystems can also be part of a larger fused aromatic or aliphatic ringsystem; the possible substituents R¹ can potentially be located on eachfree position; Aryl are identical or different on each occurrence andare each an aromatic or heteroaromatic ring system which has from 2 to40 carbon atoms and may be substituted or unsubstituted or a substitutedor unsubstituted stilbenylene or tolanylene unit; the possiblesubstituents R¹ can potentially be located on each free position; R¹ isidentical or different on each occurrence and is a straight-chain,branched or cyclic alkyl or alkoxy chain which has from 1 to 22 carbonatoms and in which one or more nonadjacent carbon atoms may also bereplaced by N—R², O, S, —CO—O—, O—CO—O, where one or more H atoms mayalso be replaced by fluorine, an aryl or aryloxy group which has from 5to 40 carbon atoms and in which one or more carbon atoms may also bereplaced by O, S or N which may also be substituted by one or morenonaromatic radicals R¹, or Cl, F, CN, N(R²)₂, B(R²)₂, where two or moreradicals R¹ may also together form a ring system; R^(a) is identical ordifferent on each occurrence and is a straight-chain, branched or cyclicalkyl or alkoxy chain which has from 1 to 22 carbon atoms and in whichone or more nonadjacent carbon atoms may also be replaced by N—R², O, S,—CO—O—, O—CO—O, where one or more H atoms may also be replaced byfluorine, an aryl or aryloxy group which has from 5 to 40 carbon atomsand in which one or more carbon atoms may also be replaced by O, S or Nwhich may also be substituted by one or more nonaromatic radicals R¹, orCl, F, CN, N(R²)₂, B(R²)₂; R² is identical or different on eachoccurrence and is H, a straight-chain, branched or cyclic alkyl chainwhich has from 1 to 22 carbon atoms and in which one or more nonadjacentcarbon atoms may also be replaced by O, S, —CO—O—, O—CO—O, where one ormore H atoms may also be replaced by fluorine, an aryl group which hasfrom 5 to 40 carbon atoms and in which one or more carbon atoms may alsobe replaced by O, S or N which may also be substituted by one or morenonaromatic radicals R¹; m is identical or different on each occurrenceand is 0, 1 or 2; o is identical or different on each occurrence and is0, 1 or 2, with the proviso that o must not be 0 when m=2; r isidentical or different on each occurrence and is 0 or 1, z is identicalor different on each occurrence and is 0, 1, 2 or 3; the open-line bondindicates the linkage in the polymer; it should in the present case notbe a methyl group.
 2. The polymer as claimed in claim 1, characterizedin that the units of the formula (I) are bound into the side chain ofthe polymer and are linked via position 2 or position 3 of the carbazoleto the main chain of the polymer.
 3. The polymer as claimed in claim 1,characterized in that the structural units of the formula (I) areincorporated into the main polymer chain via the positions 3 and 6 orthe positions 2 and 7 of the carbazole.
 4. The polymer as claimed inclaim 1, characterized in that the structural units of the formula (I)are incorporated into the polymer chain via the positions 3 and 9 of thecarbazole or via the positions 2 and 9 of the carbazole if R is an arylor heteroaryl system so that the conjugation of the chain is maintained.5. The polymer as claimed in claim 1, characterized in that furtherstructural elements are present.
 6. The polymer as claimed in claim 5,characterized in that the further structural elements are ortho-, meta-or para-phenylenes, 1,4-:naphthylenes, 9,10-anthracenylenes,2,7-phenanthrenylenes, 1,6- or 2,7- or 4,9-pyrenylenes or2,7-tetrahydropyrenylenes, oxadiazolylenes, 2,5-thiophenylenes,2,5-pyrrolylenes, 2,5-furanylenes, 2,5-pyridylenes, 2,5-pyrimidinylenes,5,8-quinolinylenes, fluorenes, spiro-9,9′-bifluorenes, indenefluorenesand indenofluorenes or heteroindenofluorenes.
 7. The polymer as claimedin claim 5, characterized in that further structural elements whichimprove charge transport and/or charge injection are present.
 8. Thepolymer as claimed in claim 7, characterized in that the furtherstructural elements are selected from the groups of triarylamines oroxadiazolylenes.
 9. The polymer as claimed in claim 5, characterized inthat the further structural elements are selected from groups whichshift the color of the emission, thus also alter the band gap of thepolymer and thus generally also of the charge injection properties orcharge transport properties.
 10. The polymer as claimed in claim 9,characterized in that the further structural elements are selected fromthe groups of arylene-vinylene or arylene-acetylene structures and/orlarger aromatic units.
 11. The polymer as claimed in claim 5,characterized in that it comprises metal complexes which make transferof singlet excitons to triplet excitons possible and which emit lightfrom the triplet state.
 12. The polymer as claimed in claim 11,characterized in that the metal complexes contain d and f transitionmetals.
 13. The polymer as claimed in claim 12, characterized in thatthe metal complexes contain metals of groups 8 to
 10. 14. The polymer asclaimed in claim 1, characterized in that the following applies to thesymbols and indices: R is identical or different on each occurrence andis an aromatic or heteroaromatic ring system selected from amongthiophene, benzothiophene, benzene, naphthalene, anthracene andphenanthrene which are unsubstituted or substituted by a substituent R¹,or a benzyl ring system whose phenyl group has the same substitutionpattern as the abovementioned systems; Aryl is identical or different oneach occurrence and is an aromatic or heteroaromatic ring systemselected from among thiophene, benzene, pyridine, fluorene,spirobifluorene, anthracene, phenanthrene, pyrene, quinoline andnaphthalene which bears from 0 to 2 substituents R¹ on the freepositions; m is identical or different on each occurrence and is 0 or 1.15. (canceled)
 16. The polymer as claimed in claim 1, characterized inthat at least two nonaromatic carbon atoms are present in thesubstituents on average per repeating unit.
 17. The polymer as claimedin claim 1, characterized in that no substituents having more than 12carbon atoms are present in a linear chain.
 18. The polymer as claimedin claim 1, characterized in that it is prepared by SUZUKI coupling,YAMAMOTO coupling, STILLE coupling, HARTWIG-BUCHWALD coupling, theWITTIG-HORNER reaction or a precursor process.
 19. A mixture of apolymer as claimed in claim 1 with further polymers.
 20. A mixturecomprising (A) 5-99.5% by weight of at least one conjugated polymer(POLY2) comprising 1-100 mol % of units of the formula (XXXII),

where the symbols and indices have the following meanings: R³ isidentical or different on each occurrence and is a linear or branchedalkyl chain which has from 1 to 40 carbon atoms and may be substitutedor unsubstituted, a cycloalkyl system which has from 3 to 40 carbonatoms and may be substituted or unsubstituted, an aromatic orheteroaromatic ring system which has from 2 to 40 carbon atoms and mayin each case be substituted or unsubstituted or an alkylenearyl,alkylenecycloalkyl or alkyleneheteroaryl system which may be substitutedor unsubstituted; the possible substituents R¹ can potentially belocated on each free position; the aryl and heteroaryl systems can alsobe part of a larger fused aromatic ring system; Aryl are identical ordifferent on each occurrence and are each an aromatic or heteroaromaticring system which has from 2 to 40 carbon atoms and may be substitutedor unsubstituted or a substituted or unsubstituted stilbenylene ortolanylene unit; the possible substituents R¹ can potentially be locatedon each free position: R¹ is identical or different on each occurrenceand is a straight-chain, branched or cyclic alkyl or alkoxy chain whichhas from 1 to 22 carbon atoms and in which one or more nonadjacentcarbon atoms may also be replaced by N—R², O, S, —CO—O—, O—CO—O, whereone or more H atoms may also be replaced by fluorine, an aryl or aryloxygroup which has from 5 to 40 carbon atoms and in which one or morecarbon atoms may also be replaced by O, S or N which may also besubstituted by one or more nonaromatic radicals R¹, or Cl, F, CN,N(R²)₂, B(R²)₂, where two or more radicals R¹ may also together form aring system; R^(a) is identical or different on each occurrence and is astraight-chain, branched or cyclic alkyl or alkoxy chain which has from1 to 22 carbon atoms and in which one or more nonadjacent carbon atomsmay also be replaced by N—R², O, S, —CO—O—, O—CO—O, where one or more Hatoms may also be replaced by fluorine an aryl or aryloxy group whichhas from 5 to 40 carbon atoms and in which one or more carbon atoms mayalso be replaced by O, S or N which may also be substituted by one ormore nonaromatic radicals R¹, or Cl, F, CN, N(R²)₂, B(R²)₂; p1 R² isidentical or different on each occurrence and is H, a straight-chain,branched or cyclic alkyl chain which has from 1 to 22 carbon atoms andin which one or more nonadjacent carbon atoms may also be replaced by O,S, —CO—O—, O—CO—O, where one or more H atoms may also be replaced byfluorine, an aryl group which has from 5 to 40 carbon atoms and in whichone or more carbon atoms may also be replaced by O, S or N which mayalso be substituted by one or more nonaromatic radicals R¹; m isidentical or different on each occurrence and is 0, 1 or 2; o isidentical or different on each occurrence and is 0, 1 or
 2. with theproviso that o must not be 0 when m=2; r is identical or different oneach occurrence and is 0 or 1, z is identical or different on eachoccurrence and is 0, 1, 2 or 3; and (B) 0.5-95% by weight of at leastone organic or organometallic dendrimer or at least one low molecularweight molecule having a molecular weight in the range <10 000 (COMP1)which in a pure or dilute film is capable of fluorescence orphosphorescence and which has adequate solubility in suitable solventsto be able to be processed in the blend together with the polymer from asolution in this solvent.
 21. The blend as claimed in claim 20,characterized in that the component COMP1 of the blend comprises one ormore metal complexes which make transfer of singlet excitons to tripletexcitons possible and which emit light from the triplet state.
 22. Themixture as claimed in claim 20, characterized in that the COMP1 containsat least one d and/or f transition metal.
 23. The mixture as claimed inclaim 22, characterized in that the COMP1 contains at least onetransition metal from groups 8 to
 10. 24. The mixture as claimed inclaim 20, characterized in that POLY2 comprises 30-100 mol % ofstructural units of the formula (XXXII).
 25. An organic integratedcircuits (O-ICs), organic field effect transistors (OFETs), organic thinfilm transistors (OTFTs), organic solar cells (O-SCs), organiclight-emitting diodes (OLEDs), organic laser diodes (O-lasers) ornonlinear optics which comprises the mixture as claimed in claim
 20. 26.An electronic component comprising one or more active layers, wherein atleast one of these active layers comprises one or more polymers asclaimed in claim
 1. 27. An electronic component as claimed in claim 26,characterized in that it is an organic light-emitting diode.
 28. Thepolymer as claimed in claim 1, characterized in that the structuralelements of the formula (I) are selected from among the formulae (II) to(XXXI) which may be substituted or unsubstituted.